Thiadiazole monoazo dyes



United States Patent Int. Cl. c09b 29/36 US. Cl. 260158 Claims This invention relates to new water-insoluble monoazo dyes having the general formula:

Dyes having the Formula I in which R denotes a methyl group or ethyl group, R denotes a hydrogen atom or a chlorine atom, R denotes a fi-cyanoethyl, fi-carbomethoxy or fl-carboethoxyethyl group and R denotes a methyl, ethyl or fi-hydroxyethyl group are of particular technical interest.

The new dyes are obtained by conventional methods by coupling diazo compounds of amines having the Formula II:

with compounds having the general Formula III:

(III) the radicals R, R R and R having the above meanings.

Examples of coupling components having the Formula 111 are:

N-ethyl-N-B-cyanoethylaminobenzene, N-B-hydroxyethyl-N-B-cyanoethylaminobenzene, N-B-carb omethoxyethyl-N-B-hydroxyethylaminobenzene, N-methyl-fi-carboethoxyethylaminobenzene, N-methyl-B-carbomethoxyethylaminobenzene, N-propyl-B-carbomethoxyethylaminobenzene, N-ethyl-fi-cyanoethyl-3-chloroaminobenzene, N-ethyl-N-fl-cyanoethyl-3-methylaminobenzene,

N-fi-cyanoethyLN-fi-hydroxyethyl-3-methylaminobenzene, N-B-cyanoethyl-N-butyl-3-methylaminobenzene, N-fl-hydroxyethyl-N-fi-cyanoethyl-3-chloroaminobenzene, N-ethyl-N-B-acetoxyethylaminobenzene, N- S-acetoxyethyl-N-B-cyanoethylaminobenzene, N-fl-acetoxyethyl-N-fi-hydroxyethylaminobenzene, N-B-methoxyethyl-N-fl-cyanoethylaminobenzene, N-fi-methoxyethyl-N-B-carbomethoxyethylaminobenzene, N-B-methoxyethyl-N-fi-acetoxyethylaminobenzene, N-B-cyanoethyl-N-B-methoxyethyl-3-methylaminobenzene.

The new dyes are eminently suitable, particularly in finely divided form, for dyeing for example fibers, filaments, threads, flock, woven fabrics and knitted fabrics of cellulose acetaate (secondary cellulose acetate and cellulose triacetate), linear polyesters and polyamides. They go on very well and dyeings obtained therewith are distinguished by good fastness properties. In many cases, the wet fastness, light fastness, resistance to gas-fume fading and thermal resistance are outstanding.

The invention is illustrated by the following examples. The parts and percentages are by weight; parts by volume bear the same relation to parts by weight as the liter (STP) to the kilogram.

EXAMPLE 1 25 parts of a mixture of glacial acetic acid and propionic acid (17:3) is allowed to drip at 0 to 5C. into a mixture of 7 parts of concentrated sulfuric acid and 7.25 parts of nitrosylsulfuric acid having a content of 13.1% of free dinitrogen trioxide (N 0 Then 5.58 parts of 3 carbomethoxyethylmercapto S-arninothiadiazole-l,2,4 is introduced at 0 to 5 C. and then at the same temperature another 25 parts of the mixture of glacial acetic acid and propionic acid (17:3) is dripped in. The Whole is stirred for three hours and any excess of free dinitrogen trioxide present is destroyed by adding 1 part of urea. A solution of 4.35 parts of N-ethyl-N-B-cyanoethylaminobenzene in 7.5 parts of methanol is allowed to flow gradually at 0 to 5 C. into the resultant clear diazo solution, the whole is stirred for thirty minutes at this temperature and the solution obtained is poured onto 250 parts of water and 250 parts of ice. The crystalline dye is suction filtered two hours later, washed with water until neutral and dried at 50 C. at subatmospheric pressure. It dyes cellulose acetate bright red shades having very good resistance to gas-fume fading and has the formula:

II HaCO-C-CHz-CHz-S- C N EXAMPLE 2 A diazo solution is prepared by the method described in Example 1 from 5.82 parts of 3-carboethoxyethylmercapto-S-aminothiadiazole-1,2,4. This is allowed to flow gradually into a solution consisting of 4.75 parts of N-B- hydroxyethyl-N-fi-cyanoethylaminobenzene, 3 parts of concentrated hydrochloric acid, 150 parts of water, parts of ice and 31 parts of anhydrous sodium acetate. The dye, isolated by a conventional method, dyes cellulose acetate neutral red shades having outstanding light fast 3 4 ness, resistance to gas-fume fading and wet fastness and Other dyes, some of them having very good to good has the formula: fastness properties on cellulose acetate or polyester, are

obtained by combination of the diazo components set ll out in the following table with the coupling components HCZO"C'CHTCHTS C w 5 indicated to form monoazo dyes, The diazotization and @m-om-om-on coupling is carried out as described in Example 1.

S CHz-CHz-OH Shade of dyeing on Example N o. Diazo component Coupling component Acetate Polyester 0 C2115 ll 3 C2H5O-CC2H4SIJ H N\ Red Red.

N 0-NH2 C H ON El) /OZH OH 4 cnao-c-cznis -l r N\ Red----.--. Red.

' N C-NHZ C2H4CN /C2H4OH 5 CzH5OCCH2--S("3 fi N\ Red Red. N C-NH2 I CZH4CN s w /C2H5 e Ha0o-002Hts 1 I N\ Pink Red.

N C-NHz C2H4CN 1130 S El) /CzHs 7 H5 z 2 4 fi @N Pink Red.

N CNH2 CZH4ON S El) /CZH CN s H5c20-002H4s( :-I N\ Scarlet Scarlet. N C-NHa C2115 0 CH3 ll 9 H CzOCCH2Sfi-Ifi N\ Red. Red.

N 0NH2 l C2H4CN Cl s g /C2H4OH 10 H COCC2H4SG[IfiI N\ Scarlet Scarlet.

N\ /CNH2 C2H4C=O s OOH; (I) /CH3 11 nscio-c-o ms l-i l N\ Red Red.

N C-NH: l C2H4CO2CH3 (H /C2H-1CN 12 cH3o-c-o2Hi-s -1 I N\ Scarlet Scarlet.

N C-NHz C2H4OfiCH3 H C2H5 13 CHaOC-C2H4SCIfi N\ Red Red.

N CNH2 CzH40fi-CH3 We claim: 1. A dye having the general formula ii RO- -CHz0H s-(H3--1| lI /m in which R denotes a member selected from the class consisting of methyl and ethyl, R denotes a member selected from the class consisting of hydrogen and chlorine, R denotes a member selected from the class consisting of ,B-cyanoethyl, ,S-carbomethoxyethyl and ,8- carboethoxyethyl, and R denotes a member selected from the class consisting of methyl, ethyl and fi-hydroxyethyl.

6 3. The dyes of the formula where R denotes a member selected from the class consisting of methyl and ethyl.

4. The dyes of the formula RO JCII2-CH2-SClfiT S CHzCHzOH Where R denotes a member selected from the class consisting of methyl and ethyl.

5. The dyes of the formula N CHzCHzCOOCH:

CHzCHzCN Where R denotes a member selected from the class consisting of methyl and ethyl.

References Cited UNITED STATES PATENTS 3,221,006 11/1965 Moore et a1. 260-158 CHARLES B. PARKER, Primary Examiner.

D. M. PAPUGA, Assistant Examiner.

U.S. Cl. X.R.

U.S. DEPARTMENT OF COMMERCE PATENT OFFICE Washington, 0.6. 20231 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3 ,441 ,554 April 29 1969 Erwin Hahn et a1.

It is certified that error appears in the above identified patent and that said Letters Patent are hereby corrected as shown below:

Columns 3 and 4, in the table, second column, that portion of the formula reading "C H OCCH should read Signed and sealed this 21st day of April 1970.

(SEAL) Attest:

Edward M. Fletcher, Jr.

Attesting Officer WILLIAM E. SCHUYLER, JR.

Commissioner of Patents 

1. A DYE HAVING THE GENERAL FORMULA 